Reaction of (TMEDA)Pt(CH 3 ) 2 with n-perfluoropropyl iodide in hexanes results in an apparent cis addition of the perfluoroalkyl iodide to give the six-coordinate Pt(IV) complex (TMEDA)Pt(n-C 3 F 7 )(CH 3 ) 2 I (6a). Complex 6a slowly and reversibly reductively eliminates CH 3 I in solution to afford an equilibrium with the Pt(II) complex (TMEDA)Pt(n-C 3 F 7 )(CH 3 ) (9a). Addition of triethylamine drives the equilibrium toward 9a. Identical reactions of perfluoroethyl iodide are observed to afford 6b and 9b. Reaction of 6a with AgBF 4 generates the cationic Pt(IV) complex [(TMEDA)Pt(n-C 3 F 7 )(CH 3 ) 2 (OH 2 )]BF 4 (11), which reacts with NaCl to form (TMEDA)Pt(n-C 3 F 7 )(CH 3 ) 2 Cl (12); both reactions retain the cis stereochemistry of the starting material 6a. Reaction of 9a with CF 3 SO 3 H in moist solvents generates the cationic Pt(II) complex [(TMEDA)Pt(n-C 3 F 7 )(OH 2 )]O 3 SCF 3 (17), which reacts with iodide to afford the neutral iodide complex (TMEDA)Pt(n-C 3 F 7 )I ( 14). Reaction of complex 9a with I 2 in hexanes results in trans addition of I 2 to generate (TMEDA)Pt(C 3 F 7 )(CH 3 )I 2 (13), which is converted to (TMEDA)Pt(n-C 3 F 7 )I ( 7) by treatment with AgBF 4 followed by NaI. Complex 14 reacts with NaBH 4 to produce (TMEDA)Pt(n-C 3 F 7 )H ( 18). The TMEDA ligand can be displaced from 9a by DPPE to give (DPPE)Pt(n-C 3 F 7 )(CH 3 ) ( 19), which reacts with CF 3 -SO 3 H to give the triflate complex (DPPE)Pt(n-C 3 F 7 )O 3 SCF 3 (20), in equilibrium with a water complex, [(DPPE)Pt(n-C 3 F 7 )(OH 2 )]O 3 SCF 3 (21). Reaction of 20 with iodide, or 19 with I 2 , gives (DPPE)Pt(n-C 3 F 7 )I ( 22), which can be converted to the hydrido complex (DPPE)Pt(n-C 3 F 7 )H ( 23) with NaBH 4 . The X-ray crystal structures of complexes 6a, 9a, 9b, 10, 13, 18, 19, 20, and 23 have been determined, and structural comparisons in terms of ligand cis and trans influences are discussed.